Synthesis of polyaniline/polytoluidine block copolymer via the pernigraniline oxidation state

Polyaniline was electrochemically synthesized in the emeraldine oxidation state and then converted to the pernigraniline oxidation state by applying an electric potential under optimized conditions. The stability/reactivity of polyaniline in the pernigraniline oxidation state was evaluated in various aqueous media. The products of the reduction of the pernigraniline oxidation state by o-toluidine were analyzed by gel permeation chromatography, ultraviolet–visible and infrared spectroscopies, and cyclic voltammetry. The results are consistent with the synthesis of a diblock copolymer of polyaniline/poly(o-toluidine) and also of some poly(o-toluidine) homopolymer in the emeraldine oxidation state as a side product.     

Corrosion performance of chemically synthesized poly(aniline-co-o-toluidine) copolymer coating on mild steel

A soluble copolymer from aniline and o-toluidine [poly(aniline-co-o-toluidine)] was synthesized by chemical oxidative copolymerization using ammonium persulphate as an oxidant in hydrochloride aqueous medium. The resultant copolymer was characterized by Fourier Transform Infrared (FTIR) spectroscopy and chemically deposited on mild steel specimens using N-methyl-2-pyrrolidone (NMP) as solvent via solution evaporation method. The anticorrosive properties of copolymer coating was investigated in major corrosive environments, such as 0.1 M HCl, 5% NaCl solution, artificial seawater, distilled water and open atmosphere by conducting various corrosion tests which include: immersion test, open circuit potential (OCP) measurements, potentiodynamic polarization measurements and atmospheric exposure test. The corrosion performance of copolymer coating was also compared separately with polyaniline (PANi) and poly(o-toluidine) (POT) homopolymer coatings. The surface morphologies of polymer coatings were evaluated using scanning electron microscopy (SEM). The synthesized copolymer exhibited excellent protection against mild steel corrosion; the protection efficiency being in the range of 78–94% after 30 days of immersion. The corrosion performance of copolymer in 5% NaCl and artificial seawater was comparable, which was only marginally better than in 0.1 M HCl. In general, the performance of copolymer coating was found to be better than that of homopolymer coatings.     

Synthesis and characterization of poly(2‐ethylaniline)–poly(styrenesulfonic acid) and poly(o‐phenetidine)–poly(styrenesulfonic acid) complexes

This research focuses on the synthesis of ethyl and ethoxy substituted polyaniline with poly(styrenesulfonic acid) comprising a poly(o‐phenetidine)–poly(styrenesulfonic acid) [P(O? P)‐PSSA] and poly(2‐ethylaniline)–poly(styrenesulfonic acid) [P(2‐E)‐PSSA]. The complexes P(O? P)‐PSSA and P(2‐E)‐PSSA were prepared by chemical polymerization of monomer (o‐phenetidine, 2‐ethylaniline) with PSSA using an oxidant of ammonium persulfate in 1M HCl solution; polyaniline (PANI), poly(2‐ethylaniline) (P2E), poly(o‐pheneditine) (POP), and polyaniline‐poly(styrenesulfonic acid) (PANI‐PSSA) also were prepared by chemical polymerization to be the reference samples. The products were characterized by IR, VIS, EPR, water solubility, elemental analysis, conductivity, SEM, and TEM. IR spectral studies shown that the structure of P(2‐E)‐PSSA and P(O? P)‐PSSA complexes is similar to that of polyaniline. EPR and visible spectra indicate the formation of polarons. The morphology of the blend was investigated by measured SEM and TEM, indicating the conducting component and electrically conductive property of the polymer complexes. The pH value for deprotonation [pH ≥ 9.5 for P(2‐E)‐PSSA and pH ≥ 8.0 for P(O? P)‐PSSA] are higher than that of corresponding HCl salts, indicating an intimate interaction between polymer chains. Elemental analysis results show that P(O? P)‐PSSA has a nitrogen‐to‐sulfur ratio of ～52%, larger than that for P(2‐E)‐PSSA, ～41%. The conductivity of the complexes is around 10^?2S/cm, and the solubility of P(2‐E)‐PSSA and P(O? P)‐PSSA in water is 2.9 and 1.9 g/L, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1198–1205, 2005     

Self-Assembly of Methyl Substituted Polyaniline Hollow Nanospheres in a Polyelectrolyte Solution

Hollow nanospheres of poly(m-toluidine), poly(o-toluidine), and poly(N-methylaniline) were successfully prepared in a solution of poly(methyl vinyl ether-alt-maleic acid) by using ammonium persulfate as the oxidant. The polymerization processes of methyl substituted aniline were monitored by recording pH and temperature changes of the reaction medium. The experimental results showed that the substitution position of methyl group affected the characteristics of formed hollow nanospheres. The formation mechanism of such hollow nanospheres was suggested. The produced hydrophobic oligomers self-assembled at the interface of water/droplet of monomers and acted as the soft template for the formation of hollow spheres.     

Comparative studies of electrochemically deposited poly(o-toluidine) and poly(m-toluidine) films

Under galvanostatic deposition conditions poly(o-toluidine) exhibits a higher rate of polymerization than poly(m-toluidine). This observation is supported by results obtained by different characterization techniques such as spectrophotometry, scanning electron microscopy and thermogravimetric analysis. The monomer concentration was found to be the predominant parameter in obtaining selectively a conducting salt phase in both cases. However, the morphology of these polymeric films does not reveal any particular relationship with monomer concentration; instead a mixed morphology, i.e. a combination of granules and fibres, is observed. Finally, the thermal stability of poly(m-toluidine) is lower than that of poly(o-toluidine) with a shift of 190°C in the final decomposition temperature.     

Corrosion protection aspects of electrochemically synthesized poly(o-anisidine-co-o-toluidine) coatings on copper

The poly(o-anisidine-co-o-toluidine) coatings were synthesized on copper substrates by electrochemical copolymerization of o-anisidine with o-toluidine using sodium salicylate as supporting electrolyte. These coatings were characterized by cyclic voltammetry, UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and scanning electron microscopy (SEM). The formation of the copolymer with the mixture of monomers in the aqueous sodium salicylate solution was ascertained by a critical comparison of the results obtained with the polymerization of the individual monomers, o-anisidine and o-toluidine, respectively. The corrosion protection aspects of poly(o-anisidine-co-o-toluidine) coatings to copper was investigated in aqueous 3% NaCl solution by potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS). The results of the potentiodynamic polarization measurements and EIS studies showed that the poly(o-anisidine-co-o-toluidine) coatings provided the effective corrosion protection to copper than that of respective homopolymers. The corrosion rate is observed to depend on the feed ratio of o-toluidine used for the synthesis of the copolymer coatings.     

Electroactive polymer films for stainless steel corrosion protection

Electroactive polymer films of polyaniline, poly-o-toluidine and a composite of both were deposited on stainless steel and their performance as protective coatings against corrosion was evaluated. Open circuit potential and potentiodynamic studies of the polymer-coated stainless steel in a corrosive medium showed a significant shift in the corrosion potential towards more positive values. Mechanical characteristics of the films were evaluated by means of microhardness measurements, revealing nonelastic films in all cases and low hardness values that increased from polyaniline to poly-o-toluidine to the composite. The best results were obtained in the case of the polyaniline-o-toluidine composite.     

Electrochemical behaviors of polyaniline–poly(styrene‐sulfonic acid) complexes and related films

This research focuses on the syntheses of polyaniline with poly(styrenesulfonic acid) and their electrochemical behavior, including absorbance behavior and electrochemical response time of polyaniline‐poly(styrenesulfonic acid) [PANI–PSSA]. The complexes PANI–PSSA were prepared by electrochemical polymerization of monomer (aniline) with PSSA, using indium‐tin oxide (ITO) as working electrode in 1M HCl solution. Polyaniline (PANI), poly(o‐phenetidine)–poly(styrenesulfonic acid) [POP–PSSA], and poly(2‐ethylaniline)–poly(styrenesulfonic acid) [P2E‐PSSA] also were prepared by electrochemical polymerization and to be the reference samples. The products were characterized by IR, VIS, EPR, water solubility, elemental analysis, conductivity, SEM, and TEM. IR spectral studies shows that the structure of PANI–PSSA complexes is similar to that of polyaniline. EPR and visible spectra indicate the formation of polarons. The morphology of the blend were investigated by SEM and TEM, which indicate the conducting component and electrically conductive property of the polymer complexes. Elemental analysis results show that PANI–PSSA has a nitrogen to sulfur ratio (N/S) of 38%, lower than that for POP–PSSA (52%) and P2E–PSSA (41%). Conductivity of the complexes are around 10^?2 S/cm, solubility of PANI–PSSA in water is 3.1 g/L. The UV‐Vis. absorbance spectra of the hybrid organic/inorganic complementary electro‐chromic device (ECD), comprising a polyaniline–poly(styrenesulfonic acid) [PANI–PSSA] complexes and tungsten oxide (WO₃) thin film coupled in combination with a polymer electrolyte poly(2‐acrylamido‐2‐methyl‐propane‐sulfonic acid) [PAMPSA]. PANI–PSSA microstructure surface images have been studied by AFM. By applying a potential of ～3.0 V across the two external ITO contacts, we are able to modulate the light absorption also in the UV‐Vis region (200–900 nm) wavelength region. For example, the absorption changes from 1.20 to 0.6 at 720 nm. The complexes PANI–PSSA, POP–PSSA, and P2E–PSSA were prepared by electrochemical polymerization of monomer (aniline, o‐phenetidine, or 2‐ethylaniline) with poly(styrenesulfonic acid), using ITO as working electrode in 1M HCl solution, respectively. UV‐Vis spectra measurements shows the evidences for the dopped polyaniline system to be a highly electrochemical response time, recorded at the temperature 298 K, and the results were further analyzed on the basis of the color‐ discolor model, which is a typical of protontation systems. Under the reaction time (3 s) and monomer (aniline, o‐phenetidine, 2‐ethylaniline) concentration (0.6M) with PSSA (0.15M), the best electrochemical color and discolor time of the PANI–PSSA is slower than POP–PSSA complexes (125/125 ms; thickness, 3.00 μm) and P2E–PSSA complexes. Under the same thickness (10 μm), the best electrochemical color and discolor time of the PANI–PSSA complexes is 1500/750 ms, that is much slower than P2E–PSSA complexes (750/500 ms) and POP–PSSA complexes (500/250 ms). In film growing rate, the PANI–PSSA complexes (0.54 μm/s) are slower than P2E–PSSA complexes (0.79 μm/s) and POP–PSSA complexes (1.00 μm/s), it can be attributed to the substituted polyaniline that presence of electro‐donating (? OC₂H₅ or ? C₂H₅₎ group present in aniline monomer. The EPR spectra of the samples were recorded both at 298 K and 77 K, and were further analyzed on the basis of the polaron–bipolaron model. The narrower line‐width of the substituted polyaniline complexes arises due to polarons; i.e., it is proposed that charge transport take place through both polarons and bipolarons, compared to their salts can be attributed to the lower degree of structural disorder, the oxygen absorption on the polymeric molecular complexes, and due to presence of electro‐donating (? OC₂H₅ or ? C₂H₅) group present in aniline monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:4023–4044, 2006     

Preparation and electrochemical behavior of dopamine-selective polymeric membrane

Summary o-toluidine was polymerized electrochemically using constant-potential electrolysis at a gold electrode surface. Electrochemical behavior of dopamine and ascorbic acid at the polymer electrode prepared in this manner was examined by cyclic and differential pulse voltammetry techniques. The influence of chemical and electrochemical variables on dopamine selectivity of the polymer electrode was systematically investigated and the optimal values for each parameter were determined. Experimental results showed that optimized polymeric membrane exhibited selectivity for dopamine while blocking ascorbic acid. Therefore, it is claimed that poly (o-toluidine) film can be used as a dopamine-selective polymeric membrane in the presence of ascorbic acid. Key Words: poly (o-toluidine); selective membrane; dopamine Received: 22 November 1999/Revised version: 25 January 2000/Accepted: 10 February 2000     

Synthesis and Characterization of a Conducting Composite of Polyaniline,Poly(o-Anisidine), and Poly(Aniline-co-o-Anisidine)

A conducting composite of polyaniline, poly(o-anisidine), and poly(aniline-co-o-anisidine) using incorporation of TiO₂ and SiO₂ was prepared by electrochemical polymerization. The films were electropolymerized in a solution containing 0.1 M monomer(s), 1 M sulfuric acid as supporting electrolyte, and 10^?5 M TiO₂ and SiO₂ by applying a sequential linear potential scan rate of 50 mV/s between ? 0.2 and 1.0 V versus an Ag/AgCl electrode. The composites were characterized by cyclic voltametry, UV-visible spectroscopy, electrical conductivity, and thermogravimetric analysis. It was observed that the UV-visible peaks appeared in the region of the conducting emerladine salt phase. In an overall study, the polymers prepared using TiO₂ had a higher conductivity than those prepared with SiO₂; however, higher conductivity was observed for the polyaniline-TiO₂ conducting composite than for the other polymers. The composites did not lose their color at higher temperature and hence can be utilized as the conductive pigments required for antielectrostatic applications.     

A correlation of electrochemical and spectroelectrochemical properties of poly(o-toluidine)

A comparative discussion of the electrochemical and spectroelectrochemical properties of poly(o-toluidine) POT, a methyl substituted derivative of polyaniline, PANI, is presented. POT exists in various oxidation states and shows an insulator to conductor transition when doped by electrooxidation. The transformation of the polymer film from its non-conducting leucoemeraldine to its conducting emeraldine state and further on to its again non-conducting pernigraniline form was observed with different techniques including cyclic voltammetry, in situ conductivity measurements and in situ UV-vis and Raman spectroelectrochemical methods. Results reveal that POT shows a good correlation between its electrochemical and spectroelectrochemical properties in its different oxidation states.     

Preparation and properties of polyimide–clay nanocomposite materials for anticorrosion application

A series of polymer–clay nanocomposite (PCN) materials that consist of organosoluble polyimide and layered montmorillonite clay were prepared by the solution dispersion technique. The organosoluble polyimide containing non‐coplanar moiety in diamine monomer and flexible bridging linkages in dianhydride monomer was synthesized by chemical imidization. The as‐synthesized PCN materials were characterized by infrared spectroscopy, wide‐angle powder X‐ray diffraction, and transmission electron microscopy. The organosoluble polyimide showed better corrosion resistance compared to polyaniline, poly(o‐ethoxyaniline) and poly(methyl methacrylate) by using a series of standard electrochemical corrosion measurements of corrosion potential, polarization resistance, and corrosion current in 5 wt % aqueous NaCl electrolyte. Polyimide–clay nanocomposite materials incorporated with low loading of clay were found to further improve corrosion inhibition over pure polyimide. Effects of the material composition on the O₂/H₂O molecular permeability, optical clarity, and thermal properties of polyimide–clay nanocomposite materials were studied by molecular permeability analysis, UV–visible transmission spectra, thermogravimetric analysis, and differential scanning calorimetry, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3573–3582, 2004     

Application of poly(<Emphasis Type="Italic">o</Emphasis>-phenylenediamine) in rechargeable cells

The electrochemical synthesis of poly(o -phenylenediamine) (PoPD) from an aqueous medium was suitably modified by controlling the switching potential to enhance the growth of the polymer. The charge–discharge data for the cell Zn/1 M ZnSO₄ (pH 4)/PoPD are presented. The polymer was modified by incorporating Pt microparticles into its matrix during electropolymerization. The PoPD-Pt composite electrode was also characterized as a cathode active material in aqueous cells.     

Interaction Study of Anionic Surfactant with Aqueous Non‐Ionic Polymers from Conductivity,Density and Speed of Sound Measurements

In the present study, we have investigated in detail the interactions of the anionic surfactant sodium dodecyl sulfate (SDS) with aqueous polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP) and various PEG + PVP mixtures at 293.15, 303.15 and 313.15 K by applying conductivity, density and speed of sound techniques. From experimentally measured data, the critical micelle concentration (CMC) values, standard free energy of micellization (ΔG_m^o), standard enthalpy of micellization (ΔH_m^o), standard entropy of micellization (ΔS_m^o), isentropic compressibilities (κ_s), apparent molar volumes (?_v) and apparent molar isentropic compressions (?_k) of SDS in aqueous polymer mixtures have been calculated. The nature of the process of micellization has been evidenced from the magnitude of ΔG_m^o, ΔH_m^o and ΔS_m^o values. The trends of variations obtained in the various parameters have been explained in terms of the electrostatic as well as hydrophobic interactions pertaining in SDS?PEG/PVP?water systems.     

Synthesis of poly(aniline‐co‐o‐toluidine) coatings and their corrosion‐protection performance on low‐carbon steel

Strongly adherent poly(aniline‐co‐o‐toluidine) coatings were synthesized on low‐carbon‐steel substrates by the electrochemical copolymerization of aniline with o‐toluidine with sodium tartrate as the supporting electrolyte. These coatings were characterized with cyclic voltammetry, ultraviolet–visible absorption spectroscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and scanning electron microscopy. The formation of the copolymer with the mixture of monomers in the aqueous sodium tartrate solution was ascertained by a critical comparison of the results obtained from the polymerizations of the individual monomers, aniline and o‐toluidine. The optical absorption spectrum of the copolymer was drastically different from the spectra of the respective homopolymers, polyaniline and poly(o‐toluidine). The extent of the corrosion protection offered by poly(aniline‐co‐o‐toluidine) coatings to low‐carbon steel was investigated in aqueous 3% NaCl solutions by open‐circuit‐potential measurements and a potentiodynamic polarization technique. The results of the potentiodynamic polarization measurements showed that the poly(aniline‐co‐o‐toluidine) coatings provided more effective corrosion protection to low‐carbon steel than the respective homopolymers. The corrosion rate depended on the feed ratio of o‐toluidine used for the synthesis of the copolymer coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:1868–1878, 2007     

Light reflection at polyaniline films and its application to a kinetic study of polymer chain conformation

Light reflection at polymer-coated electrodes is studied for polyaniline, poly(o-methylaniline), and poly(o-methoxyaniline). Reflected light intensity is found to be affected greatly by the applied potential for the two reasons: one is absorption of light due to coloring of the oxidized polymer film and the other is light scattering which is concerned with a polymer chain conformation upon oxidation. A new method based on the potential dependence of light reflection is proposed for studying kinetics of conformational changes of polymer chains. The rate constants evaluated are in the range of 0.05-8 s⁻¹ at room temperature, depending on the sort of polymers, the film thickness, and pH of the solution. Irrespective of the sort of polymers, the increase in film thickness or solution pH leads to the decrease of the rate constant. It is found that a film morphology has a significant effect on the rate constant, as confirmed by a comparison of rate constants observed with polyaniline films grown at different rates.     

Electrochemical synthesis and characterization of poly(pyrrole-co-o-toluidine)

The electrochemical polymerization of o-toluidine has been investigated in oxalic acid solution. It was shown that the oxidation of monomer could be achieved but this process does not yield a stable, homogenous polymer film on either platinum or mild steel electrodes. Therefore the copolymerization between pyrrole and o-toluidine has been studied as an alternative method for obtaining good quality coating (low permeability and water mobility, high stability), which could also be easily synthesized on steel. For this aim, various monomer feed ratio solutions of pyrrole:o-toluidine 9:1, 8:2 and 7:3 have been examined, in aqueous oxalic acid solution. By using cyclic voltammetry technique, copolymer films were realized on platinum and steel, successfully. The temperature of synthesis solution was found to have a vital role on polymerization and film growth, as much as the monomer feed ratio. The synthesis of homogenous copolymer film could only be achieved under ≤25 °C conditions with using the 9:1 ratio, while the 8:2 ratios could only produce stable films below 5 °C. As the amount of o-toludine increased the required temperature value decreased further, 7:3 ratio could only give a stable copolymer film below 2 °C. The characterization of deposited copolymer coating has been realized by using SEM micrographs, UV–vis and FT-IR spectroscopy techniques and cyclic voltammetry. The protective behaviour of these coatings was also investigated against mild steel corrosion in 3.5% NaCl solution, by means of electrochemical impedance spectroscopy (EIS) and anodic polarization curves. It was found that the monomer feed 8:2 ratio gave the most effective coating against the corrosion of mild steel.     

Covalent immobilization of glucose oxidase to poly(O‐amino benzoic acid) for application to glucose biosensor

A biosensor for glucose utilizing glucose oxidase (GOX) covalently coupled to poly(o‐amino benzoic acid) (PAB; a carboxy‐group‐functionalized polyaniline) is described. Amperometric response measurements conducted via unmediated and mediated (with ferrocene carboxylic acid and tetrathiafulvalene) reoxidation of GOX show that glucose can be detected over a wide range of concentrations. An enzyme‐conducting polymer‐mediator model provides for better charge transport in a biosensor. The optimal response, obtained at pH 5.5 and 300 K, lies in the 1–40 mM range. A kinetic plot yields the value of the apparent Michaelis–Menten constant, K_m^app. The operational stability of the PAB‐based glucose biosensor was experimentally determined to be about 6 days. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 662–667, 2000     

Preparation and identification of a soluble copolymer from pyrrole and o-toluidine

A series of copolymers were prepared by chemically oxidative polymerization of pyrrole (PY) and ortho-toluidine (OT) in HCl aqueous medium. The yield, intrinsic viscosity, and solubility of the copolymers were studied by changing the monomer molar ratio. The resulting PY/OT copolymers were identified by FTIR, ¹H–NMR, DSC, and WAXD techniques. The experimental results showed that the oxidative polymerization of pyrrole and o-toluidine is exothermic and the resulting polymers exhibit an enhanced solubility in most organic solvents compared with that of pyrrole homopolymer. The polymer obtained is a real and amorphous copolymer containing pyrrole and o-toluidine units. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 510–518, 2001     

Solid state polymerization of bis(trichlorophenoxo) cobalt(ii) complex to give poly(dichlorophenylene oxide)

Synthesis of four-coordinated (tetrahedral) trichlorophenol cobalt(II) complex with neutral ligand pyridine was achieved from the aqueous solution and its characterization was performed by UV-visible, IR spectral and CHN analysis. Solid state thermal polymerization of the complex was accomplished first at constant temperature employing different time intervals and secondly at constant decomposition time. The poly(dichlorophenylene oxide)s so synthesized were characterized by IR, ¹H NMR and ¹³C NMR spectral analysis, T_g determination, as well as measurement of molecular weight by a viscometric method.